Fibre-reactive dyestuffs

ABSTRACT

The invention is related to compounds of formula (I) ##STR1## their salts and mixtures thereof wherein the symbols are as defined in the specification are useful as fibre-reactive dyestuffs for dyeing or printing hydroxy-group-containing or nitrogen-containing organic substrates.

This application is concerned with phthalocyanine fibre-reactivedyestuffs and methods of producing the same.

The invention provides in one of its aspects compounds of formula (I)##STR2## their salts and mixtures thereof wherein,

R₁ is hydrogen, or a hydrocarbon group having from 1 to 8 carbon atomsoptionally comprising a hetero-atom or atoms, i.e oxygen nitrogen orsulphur atoms, in particular C₁₋₄ alkyl optionally substituted with anhydroxyl group, e.g. methyl, ethyl and hydroxyethyl

R₂ is, independently of R₁, any of the significances of R₁, or is agroup --A_(n) SO₂ --B or --A_(n) SO₂ --B' wherein B is selected from anyof the groups according to the formula

    --CH═CH.sub.2, --CH.sub.2 CH.sub.2 --Y, --CH═CH--Y or --CH(CH.sub.2 Y)--CH.sub.2 Y

wherein Y represents a hydroxyl group or a group selected from halogen,e.g. chlorine or bromine, --OSO₃ H or --SO₃ H, --OPO₃ H₂, --SSO₃ H,--OCOCH₃, --OCOC₆ H₅, --OCO(CH₂)₂ --COOH, --OCO--CH═CH--COOH, --OCO--C₆H₄ --COOH, --OCO--COOH, --OSO₂ CH₃, a quaternary nitrogen group, e.g.,--⁺ N(CH₃)₃ and a pyridinium ion or bivalent groups--OCO--COO--,--OCO--(CH₂)₂ --COO--, --OCO--CH═CH--COO-- and OCO--C₆ H₄--COO--,

B' is --(CH₂)₂ --OSO₃ H and

A_(n) is A₁ to A₃ wherein

A₁ is a group ##STR3## wherein * is a bond connected to SO₂ B and R₃ isa direct bond or is --(CH₂)₂ --,

A₂ is a group A₁, in which R₃ is a direct bond, or is an alkylene oroxyalkylene group having from 2 to 4 carbon atoms, and

A₃ is a group represented by the formula ##STR4## (wherein * is a bondconnected to SO₂ B) R₁, and R₂ together represent a divalent group, e.g.alkylene or aralkylene optionally bearing a heteroatom, i.e. oxygen,nitrogen or sulphur, preferably --(CH₂)₂ --O--(CH₂)₂ --, --(CH₂)₄₋₅ --or --(CH₂)₂ --N(R₄)--(CH₂)₂ -- wherein R₄ is an alkyl group having 1 to4 carbon atom optionally substituted with a hydroxyl group,

R_(a) is hydrogen, alkyl having 1 to 4 carbon atoms, hydroxyalkyl having2 to 4 carbon atoms or a group --A_(x) SO₂ --B wherein B is ashereinabove defined and A_(x) is defined below,

RG is a group containing a fibre-reactive group and is selected from--A_(x) SO₂ --B or --D--NR₁₀ Z

wherein A_(x) is represented by a divalent hydrocarbon group which maycomprise oxygen, nitrogen or sulphur atoms and is preferably a divalentgroup chosen from an alkylene group optionally comprising an oxygen,nitrogen or sulphur atom or atoms, e.g.--(CH₂)--₂,3, --(CH₂)--₂O--(CH₂)--₂,3 ; an aza-alkylene group --(CH₂)₂ --NR₄ --(CH₂)₂ --; anarylene group, for example ##STR5## wherein R₅ represents a hydrogenatom, halogen atom, e.g. Cl or Br, an alkyl group having 1 to 4 carbonatoms, an alkoxy group having 1 to 4 carbon atoms, --SO₃ H or --COOH,more preferably H, --COOH or SO₃ H, most preferably H or SO₃ H; aheterocyclic group, e.g. a phenylene azophenylpyrazolaryl groupaccording to the formula ##STR6## wherein R₅ is as hereinbefore definedand R₆ is a methyl group or a group --COOH; or a triazine groupaccording to the formula ##STR7## wherein L is a hydroxyl group, ahalogen atom, e.g. F, Cl or Br, or an amino group NR₁ R'₂ wherein R'₂ isany of the significances of R₁ or together with R₁ is divalent group,e.g. alkylene or aralkylene optionally bearing a hetero atom i.e.oxygen, nitrogen or sulphur, or a pyridinium group ##STR8## wherein R₉is --SO₃ H or --COOH, preferably L is a hydroxyl group, F, Cl or a group##STR9## R₇ is a divalvent group selected from alkylene, oxaalkylene,arylene or aralkylene, preferably R₇ is an alkylene group having 2 to 6carbon atoms, 3-oxapentylene or a phenylene group substituted at itsmeta or para- position with, e.g. an alkyl group, alkoxy group, COOH orSO₃ H.

R₈ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or ahydroxyalkyl group having 2 to 4 carbon atoms, preferably R₈ is ahydrogen atom, Z represents a heterocyclic fibre-reactive radical, e.g .halo-triazine or halo-pyrimidine having a labile fluorine or chlorineatom, R₁₀ is H or CH₃ and D represents a divalent group selected from##STR10## preferably when D is D₂ , R₁₀ is CH₃ M is AlOH or AlCl

Pc is a phthalocyanine radical

a is 1, 2 or 3

b is 0, 1, 2 or 3

c is 0, 1 or 2 and

a+b+c has a value which is greater than or equal to 3 and less than orequal to 4 and b and c cannot be zero at the same time,

the compounds being selected from those satisfying the followingconditions:

i) when c is 1 or 2, RG is --D--NR₁₀ Z and D is D₁, then b is 1 or 2, R₂is --A₂ SO₂ --B and R_(a) is not A_(x) SO₂ --B,

ii) when c is 1, RG is --D--NR₁₀ Z and D is D₂ or D₃, then b is 1 or 2,R₂ is --A₂ SO₂ --B and R_(a) is not A_(x) SO₂ --B,

iii) when c is 1, RG is --D--NR₁₀ Z and D is D₁ then b is 1, R₂ is --A₃SO₂ --B and R_(a) is not A_(x) SO₂ --B,

iv) when c is 1 and RG is A_(x) SO₂ --B, then R₂ is, independently ofR₁, any of the significances of R₁, b is 0, 1 or 2 and

v) when c is zero, then b is 1, 2 or 3, R₂ is A₁ SO₂ --B'

The heterocyclic fibre-reactive radical of the compounds according tothe invention are preferably selected from those fibre-reactive radicalsZ₁ to Z₉ defined hereinbelow ##STR11##

The fibre-reactive radical is preferably Z₁, Z₃ or Z₇, more preferablyZ₁. In a dyeing process, the nature of the group Z employed depends uponthe temperature at which the dyeing is to be carried out. When thedyeing temperature is from 30° to 80° C., in particular 50° to 80° C.,more particularly 50° to 60° C., it is appropriate to select Z as Z₃,Z₄, Z₅ or Z₈, in particular Z₃ or Z₇. When the dyeing temperature isfrom 80° to 100° C., it is appropriate to select Z₁, Z₂, Z₆ or Z₉, inparticular Z₁.

In a preferred embodiment of the invention there are provided compoundsaccording to the formula (Ia) ##STR12## their salts and mixtures thereofwherein A_(x), M, Pc, R_(a), R₁ and R₂ together and B are as hereinabovedefined, R₁ and R₂ are independently H, or a hydrocarbon group having1-8 carbon atoms which optionally comprise a hetero atom or atoms, i.e.oxygen, nitrogen or sulphur atoms, preferably hydrogen or alkyl groupshaving 1 to 4 carbon atoms, e.g. methyl or ethyl, or hydroxyethyl groupsand a has a value of 1, 2 or 3 and b has a value of 0, 1 or 2 providedthat a+b is not greater than 3.

In another preferred embodiment of the invention there are providedcompounds of the formula (Ib) ##STR13## their salts and mixturesthereof, wherein Pc, A₁, R₁, M and B' are as hereinabove defined and R₁is preferably H or C₁₋₄ alkyl, more preferably H or methyl,

a is 1, 2 or 3,

b is 1, 2 or 3 and,

a+b is a value of 3 or 4.

Preferred compounds according to the formula (Ib) are represented by theformulae, ##STR14## and their salts.

In another preferred embodiment of the invention there are providedcompounds according to the formula (Ic) ##STR15## their salts andmixtures thereof wherein the symbols Pc, Z, A₂, R₁ and B are ashereinabove defined, R₁₁ is hydrogen or --SO₃ H, a is 1 or 2 c is 1 or 2and b is 1 or 2, provided that a+b+c is 3 or 4.

With respect to the compounds (Ic), a preferred group A₂ is representedby phenylene, --(CH₂)_(n) --, wherein n is 2 or 3 or --(CH₂)₂--O--(CH₂)₂ -- and a preferred group B is represented by --CH₂ CH₂ OSO₃H, CH₂ CH₂ Cl or --CH═CH₂, more preferably A₂ is phenylene when B is--CH₂ CH₂ OSO₃ H and A₂ is --(CH₂)_(n) --, wherein n is 2 or 3 or--(CH₂)₂ --O--(CH₂)₂ -- when B is --CH₂ CH₂ Cl or --CH═CH₂.

It is preferred that the group --NR₁₀ Z is located at the 3- or 4-position. Similarly, when A₂ is a phenylene group it is preferred if thegroup --SO₂ B is located in the 3- or 4- position.

In a further preferred embodiment of the invention there are providedcompounds according to the formula (Id) ##STR16## their salts andmixtures thereof wherein the symbols Z, B, Pc, M, A_(n), R₁₀ are ashereinabove described, D is D₂ or D₃ and a has a value of 1 or 2.

In preferred compounds (Id) the group --SO₂ B is in the 3- or4-position.

In more preferred compounds (Id), the group A_(n) is A₁, D is D₂, B is--CH₂ CH₂ OSO₃ H or --CH═CH₂ and Z is Z₅ ; A_(n) is A₁, D is D₃, B is--CH₂ CH₂ OSO₃ H and Z is Z₅ or Z₉.

It is to be understood that the compounds of the formula (I) areobtained as isomeric mixtures according to the number and position ofthe substituents attached to the phthalocyanine ring. Particularlypreferred isomeric mixtures contain not less than 1 and not more than 2reactive groups per molecule on average, e.g. 1.0, 1.5 or 2.0. Ifdesired, one could resolve the mixtures into isomerically pure formsemploying conventional separation techniques.

When compounds according to the formula I are in the salt form, thecation associated with a sulpho-group may be any of the knownnon-chromophoric cations. Preferred are the alkali metal cations, forexample sodium or potassium. Cations associated with sulpho-groups maybe the same or different, i.e. the compounds of formula (I) can be inthe mixed-salt form.

The compounds (Ia) are formed according to a process comprising thesteps of reacting a compound of the formula (IIa) ##STR17## with oneequivalent of HNR_(a) --A_(x) --SO₂ --B and b equivalents of HNR₁ R₂ andthereafter hydrolysing the remaining SO₂ Cl group or groups, wherein R₂is selected from hydrogen, a saturated hydrocarbon group having 1 to 8carbon atoms which optionally comprise a hetero atom or atoms, i.e.oxygen, nitrogen or sulphur atoms. Preferred groups R₁ and R₂ arehydrogen or alkyl groups having 1 to 4 carbon atoms, e.g. methyl orethyl, or hydroxyethyl groups, a is 1, 2 or 3, b is 0,1 or 2 and a+b isnot greater than 3.

The sequence in which the reagents HNR_(a) --A_(x) --SO₂ --B and HNR₁ R₂are reacted is critical when A_(x) contains aromatic functionality. Inany case, it is generally preferred if the reaction proceeds initiallywith the reaction of one equivalent of HNR_(a) --A_(x) --SO₂ --Bfollowed by b equivalents of HNR₁ R₂.

Reaction of a compound IIa with HNR,--A_(x) --SO₂ --B is preferablycarried out at a pH of from 3 to 7 and at a temperature of from 0° to40° C. Reaction of HNR₁ R₂ with the product of the afore-mentionedreaction is preferably conducted at a pH of from 5 to 9 and at atemperature of from 0° to 40° C. Preferably, the reactions are carriedout in aqueous media.

The hydrolysis step is carried out in an aqueous medium under acidicconditions and is preferably carried out at a pH of from 0 to 4 and at atemperature of 0° to 20° C.

When the group A_(x) contains an azo chromophore it is preferred toemploy a modification of the process hereinabove described comprisingthe steps of reacting a compound of the formula (IIa) ##STR18## with oneequivalent of HNR_(a) --A_(x) '--NH₂ and b equivalents of HNR₁ R₂ andhydrolysing the remaining SO₂ Cl group or groups to form an intermediatecompound according to the formula (IIla), wherein R₂ is selected fromhydrogen, a saturated hydrocarbon group having 1 to 8 carbon atoms whichoptionally comprise a hetero atom or atoms, i.e. oxygen, nitrogen orsulphur atoms. Preferred groups R₁ and R₂ are hydrogen or alkyl groupshaving 1 to 4 carbon atoms, e.g. methyl or ethyl, or hydroxyethylgroups, ##STR19## wherein A_(x) '--NH₂ represents a precursor of A_(x)such that when A_(x) '--NH₂ is diazotised and the diazonium salt thusformed is coupled with a suitable coupling component the group --A_(x)--SO₂ --B is formed.

The primary amino group connected to A_(x) ' of the compound (IIIa) isdiazotised according to conventional methods and the resultant diazoniumsalt coupled with a suitable coupling component, for example ##STR20##to form a compound according to the formula (Ia). ##STR21## whereinA_(x) ' represents ##STR22## Similarly, when the group A_(x) contains atriazine group, an intermediate compound (IIIa) ##STR23## is formedwhich is thereafter reacted with a compound according to the formula##STR24## wherein at least two L are represented by fluorine orchlorine, more preferably fluorine and A_(x) ' represents R₇ to form acompound ##STR25## which in turn is reacted with one equivalent of HNR₈--R₇ --SO₂ B according to conventional methods to form a compoundaccording to the formula (Ia). ##STR26##

Compounds according to the formula (Ia) may be isolated from thereaction medium according to known methods, for example, salting outwith an alkali metal salt, filtering and drying optionally in vacuo atslightly elevated temperature.

The compounds (Ib) are formed according to a process comprising thesteps of reacting the compound

     MPc!--(SO.sub.2 Cl).sub.a+b                               (IIb)

with the compound

    HNR.sub.1 --A.sub.n --SO.sub.2 --B'                        (IIIb)

and thereafter hydrolysing the remaining --SO₂ Cl group or groupswherein B' is as hereinabove defined and a+b is 3 or 4.

Reaction of a compound (IIb) with compound (IIIb) is preferably carriedout at a pH of from 3 to 7 and at a temperature of from 0° to 40° C.Preferably the reaction is carried out in an aqueous medium.

The hydrolysis step is carried out in an aqueous medium under acidicconditions most preferably at a pH of 0 to 4 and a temperature of 0° to20° C.

Compounds according to the formula (Ib) can be isolated from thereaction medium according to known methods, for example, by salting outwith an alkali metal salt and thereafter filtering and drying optionallyunder vacuum.

The compounds according to the formula (Ic) are formed according to aprocess comprising the steps of reacting a compound having the formula(IIa) hereinabove defined with b equivalents of HNR₁ --A₂ --SO₂ B and cequivalents of a compound according to the formula (IIc) ##STR27##hydrolysing the remaining SO₂ Cl group or groups and thereaftercondensing the free amino group with a compound Z--Cl or Z--F.

Preferably, when Z is the chloro- or fluoro- triazine corresponding toZ₁, Z₂, Z₇ or Z₈, the process comprises the additional step of reactingthe condensation product with one equivalent of ammonia (when Z is Z₁)or the amine corresponding to the amine radical of Z₂, Z₇ or Z₈.

The process conditions for condensing the amine HNR₁ --A₂ --SO₂ B andthe hydolysis of any SO₂ Cl groups are conventional in the art and arepreferably as hereinabove described.

The compounds according to the formula (Id) are formed according to aprocess comprising the steps of reacting a compound having the formula(IIa) hereinabove defined with b equivalents of HNR₁ --A_(n) --SO₂ B andc equivalents of a compound according to the formula (IId) ##STR28##hydrolysing the remaining SO₂ Cl group or groups and thereafterdiazotising the free amino group before reacting the diazonium salt in acoupling reaction with a coupling component selected from ##STR29## andthereafter reacting the amino group on the radical of the couplingcomponent with a compound Z--F or Z--Cl.

The reaction conditions for condensing the amine HNR₁ --A₂ --SO₂ B andthe hydolysis of any SO₂ Cl groups are conventional in the art and arepreferably as hereinabove described. The reaction conditions for theformation of the diazonium salt are also conventional in the art.

Depending on the reaction and isolation conditions, compounds of theformula (I) may be obtained in free-acid or preferably in salt form ormixed salt form, containing, for example, one or more of the abovementioned cations. Compounds of the formula (I) may be converted fromthe free-acid form to the salt-form and vice versa using techniquesknown in the art.

Compounds according to the formula (I) their salts or a mixture thereofare useful as fibre-reactive dyestuffs. They are suitable for dyeing orprinting hydroxy-group-containing or nitrogen-containing organicsubstrates.

Accordingly, in another aspect of the invention there is provided aprocess of dyeing or printing hydroxy-group-containing ornitrogen-containing organic substrates wherein the dyeing or printing iscarried out with compounds according to the formula (I), their salts orwith mixtures thereof.

Preferred substrates may be selected from leather, and fibrous materialscomprising natural or synthetic polyamides and more particularly naturalor regenerated cellulose, e.g., cotton, viscose and spun rayon. The mostpreferred substrates are textile materials consisting of or containingcotton.

The compounds of formula (I), their salts or mixtures thereof may beemployed in dyebaths or in printing pastes and dyeing or printing may beeffected in accordance with methods known in the fibre-reactivedyestuffs field, for example, the exhaust dyeing process, padding, e.g.,Pad-steam, pad-thermofix, pad-dry, pad-batch, pad-jig and pad-roll andconventional printing or ink-jet methods. Preferably dyeings are carriedout using the exhaust dyeing method at temperatures within the range of30° to 95° C., more preferably 40° to 70° C. A goods to liquor ratio offrom 1:20 to 1:4, more preferably 1:10 to 1:6 is used.

In yet another aspect of the invention there is provided the use ofcompounds according to the formula (I), their salts or mixtures thereofin dyeing or printing substrates as hereinabove described.

The compounds according to the invention and their salts have goodcompatibility with known fibre-reactive dyestuffs. Accordingly, thecompounds of the invention, their salts or mixtures thereof may be usedalone in a dyeing or printing process or as a component in a combinationdyeing or printing composition comprising other reactive dyestuffs ofthe same class, that is, reactive dyes which possess comparable dyeingproperties, e.g., fastness properties and the extent of the ability toexhaust from a dyebath onto a substrate. In particular, the dyestuffs ofthe invention may be employed in conjunction with certain otherdyestuffs having suitable chromophores and the same or other suitablereactive groups, the proportions of a particular dyestuff in such acomposition being dictated by the particular shade which is to beproduced.

Compounds of the formula (I) and their salts display high exhaust andfixation yields. Moreover, any unfixed dyestuff is easily washed off thesubstrate. The build-up power of the compounds and their salts is alsogood. Dyeings and prints obtained exhibit good light fastness propertiesand general wet fastnesses such as fastness to washing, sea water andsweat. They are also resistant to oxidative influences, e.g. chlorinatedwater, hypochlorite bleach and peroxide, percarbonate or perboratecontaining washing liquors.

In another aspect of the invention there is provided anhydroxy-group-containing or nitrogen-containing organic substrate dyedor printed with compounds of formula (I), their salts or a mixturetherof.

There now follows a series of examples which serve to illustrate theinvention. In the examples, all parts are expressed as parts by weight,all temperatures are expressed as degrees celsius unless specificallyindicated to the contrary and λmax/nm are measured in water.

EXAMPLE 1

20 parts of PcAlCl. 2H₂ O were stirred in 140 parts of chiorosulphonicacid for 30 minutes at 20° to 25° C. The reaction mixture was thenheated to 135° to 140° C. over 2 hours. After 4 hours the reactionmixture was cooled to room temperature using, an ice bath. Thesuspension thus formed was filtered and washed in ice water to removeexcess acid.

97 parts of the product formed by the above reaction was stirred in 300parts of water and 100 parts of ice. Thereafter, a solution of 17.2parts of (2'-amino ethane-1'-sulfonyl)-2-chloroethane in 100 parts ofice water was added. The pH of the resultant solution which was 1-2 wasincreased to 4-5 with 20% sodium hydroxide and thereafter left for 15hours at a temperature of from 0° to 5° C. The resultant dyestuff wassalted out with sodium chloride, filtered and dried at a temperature offrom 40° to 50° C. ##STR30##

The dyestuff dyed cellulosic material, in particular cotton, tobrilliant green shades with excellent wet fastness.

EXAMPLE 2

The dyestuff of Example 1 was dissolved in 0.1N sodium hydroxide.Thereafter the mixture was neutralised and the product was salted-outwith sodium chloride to provide the vinyl sulphone (2) . ##STR31##

EXAMPLE 3a

97 parts of the chloroaluminium phthalocyanine sulphochloride obtainedby a process described in the first paragraph of Example 1 was stirredin 300 parts of water and 100 parts of ice and thereafter was added asolution of 16.7 parts of (2'-aminopropane-1'-sulphonyl)-ethane-2-ol in100 parts of ice water. The pH of the resultant solution which was 1-2was adjusted to 7 with 20% sodium hydroxide and the mixture reacted for4 hours at a temperature of from 0° to 5° C.

7 parts of a 25% ammoniacal solution was added to the reaction mixtureand the pH was maintained at 7 with 20% sodium hydroxide solution. Thereaction mixture was then left for a further 10 hours without coolingwhereupon the pH increased to 10-11. The reaction mixture was thenstirred for a further 2 hours at 60° C. to form the product 3a as aprecipitate which could be filtered off. Compound 3a, was isolated inits sodium salt form. ##STR32##

The compound 3a was converted into its sulphuric acid half ester bydissolving it in sulphuric acid. The resultant solution was stirred forone hour before being poured onto crushed ice. The pH was adjusted to 4to 5 by adding sodium carbonate and the reactive dye 3b was isolated byspray drying. ##STR33##

This dyestuff dyed cotton to a brilliant green shade and dyeingdisplayed high fastness properties.

EXAMPLES 4-23

The following compounds were obtained by processes analogous to theprocesses described in Examples 1 to 3.

                                      TABLE 1                                     __________________________________________________________________________     ##STR34##                                                                    Ex.                                                                              X  a b NR.sub.1 R.sub.2                                                                        R.sub.a    A.sub.x  B                                     __________________________________________________________________________    4  OH 2 1 NH.sub.2  H          CH.sub.2 CH.sub.2                                                                      CHCH.sub.2                            5  OH 2 1 NH.sub.2  H          CH.sub.2 CH.sub.2                                                                      CH.sub.2 CH.sub.2 Cl                  6  OH 2 1 NH.sub.2  H          CH.sub.2 CH.sub.2 CH.sub.2                                                             CHCH.sub.2                            7  OH 2 1 NH.sub.2  H          CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                   CH.sub.2 CH.sub.2 Cl                  8  Cl 2 1 NH.sub.2  H          CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                   CHCH.sub.2                            9  OH 2 1 NH.sub.2  CH.sub.2 CH.sub.2 SO.sub.2 CHCH.sub.2                                                    CH.sub.2 CH.sub.2                                                                      CHCH.sub.2                            10 OH 2 1 NHCH.sub.3                                                                              H          CH.sub.2 CH.sub.2                                                                      CH.sub.2 CH.sub.2 Cl                  11 OH 2 1 NH.sub.2  H                                                                                         ##STR35##                                                                             CH.sub.2 CH.sub.2 Cl                  12 OH 2 1 NH.sub.2  H                                                                                         ##STR36##                                                                             CHCH.sub.2                            13 OH 2 1 NHCH.sub.2 CH.sub.2 OH                                                                  H          CH.sub.2 CH.sub.2                                                                      CHCH.sub.2                            14 OH 2 1 NHCH.sub.2 CH.sub.2 OSO.sub.3 H                                                         H          CH.sub.2 CH.sub.2                                                                      CH.sub.2 CH.sub.2 OSO.sub.3 H         15 OH 2 1 NHCH.sub.2 CH.sub.2 SO.sub.3 H                                                          H          CH.sub.2 CH.sub.2                                                                      CHCH.sub.2                            16 OH 2 1 N(CH.sub.3)CH.sub.2 CH.sub.2 SO.sub.3 H                                                 H          CH.sub.2 CH.sub.2                                                                      CHCH.sub.2                            17 OH 2 1 Morpholino                                                                              H          CH.sub.2 CH.sub.2                                                                      CHCH.sub.2                            18 OH 2 1 N(CH.sub.3)CH.sub.2 CH.sub.2 OH                                                         H          CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                   CHCH.sub.2                            19 OH 2 1 NHCH.sub.2 CH.sub.2 CH.sub.2 OH                                                         H          CH.sub.2 CH.sub.2                                                                      CHCH.sub.2                            20 OH 2 0 --        H          CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                   CHCH.sub.2                            21 OH 2 0 --        H          CH.sub.2 CH.sub.2                                                                      CHCH.sub.2                            22 OH 3 0 --        H          CH.sub.2 CH.sub.2 CH.sub.2                                                             CH.sub.2 CH.sub.2 Cl                  23 OH 3 0 --        H          CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                   CH.sub.2 CH.sub.2 Cl                  __________________________________________________________________________

EXAMPLE 24

In an analogous process to that of Example 1, 28.1 parts of3'-aminobenzosulphonyl)-2-sulphatoethane were substituted for(2'-aminoethane-1'-sulphonyl)-2-chloroethane used in Example 1 to obtaina dyestuff having the formula 24 ##STR37##

This dyestuff dyed cotton to brilliant green shades and dyeingsdisplayed good fastness properties.

EXAMPLE 25

By dissolving dyestuff 24 in 0.1N sodium hydroxide and thereafterneutralising and isolating the product obtained therefrom, dyestuff 25was formed. ##STR38##

In the alternative, this dyestuff was formed directly by employing, in amethod according to Example 1, 18.3 parts of(3'-aminobenzol-1'-sulphonyl)-ethene instead of(2'-aminoethane-1-sulphonyl)-2-chloroethane.

EXAMPLE 26 a

In a process analogous to Example 3a, one employed 20.1 parts of(4'-aminobenzol-1'-sulfonyl)-ethane-2-ol instead of(2'aminopropane-1'-sulfonyl)-ethane-2-ol to obtain the hydroxy compound26a. ##STR39##

EXAMPLE 26 b-d

Starting from the compound 26a, the reactive dye 26b was prepared by thefollowing method: 106 parts of finely ground hydroxy dyestuff 23a weresuspended in 500 parts of thionyl chloride and the mixture heated to theboil. After evolution of gas had ceased, excess thinyl chloride wasdistilled off. The residue was dissolved in water and the pH adjusted to5-6 with sodium carbonate. The reactive dye 26b was salted out withsodium chloride.

The reactive dye 26c was obtained according to a process analogous withExample 3b.The vinyl sulphone dyestuff 26d was obtained according to amethod described in Example 2. ##STR40##

EXAMPLES 27-44

By processes analogous to those described above, other fibre-reactivedyestuffs 27-44 can be produced.

                                      TABLE 2                                     __________________________________________________________________________     ##STR41##                                                                    Ex. X  a  b NR.sub.1 R.sub.2                                                                         R.sub.4 (Pos.)                                                                     SO.sub.2 B (Pos.)                                 __________________________________________________________________________    27  OH 2  1 NH.sub.2   H    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(3)         28  OH 2  1 NH.sub.2   H    SO.sub.2 CHCH.sub.2 (3)                           29  OH 2  1 NHCH.sub.2 CH.sub.2 OH                                                                   H    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(4)         30  OH 2  1 NHCH.sub.2 CH.sub.2 OH                                                                   H    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(3)         31  OH 2  1 NHCH.sub.2 CH.sub.2 SO.sub.3 H                                                           H    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(4)         32  OH 2  1 N(CH.sub.3)CH.sub.2 CH.sub.2 SO.sub.3 H                                                  H    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(3)         33  OH 2  1                                                                                ##STR42## H    SO.sub.2 CHCH.sub.2 (4)                           34  OH 2  1 N(CH.sub.3)CH.sub.2 CH.sub.2 OH                                                          H    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(4)         35  OH 2  1 N(CH.sub.3)CH.sub.2 CH.sub.2 OH                                                          H    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(3)         36  OH 2  1 NHCH.sub.2 CH.sub.2 (OH)CH.sub.3                                                         H    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(4)         37  OH 2  1 NHCH.sub.2 CH.sub.2 CH.sub.2 OH                                                          H    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(4)         38  OH 2  1 NHCH.sub.2 CH.sub.2 CH.sub.2 OH                                                          H    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(3)         39  OH 2  1 NHCH.sub.2 CH.sub.2 COOH                                                                 H    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(4)         40  OH 1  O --         SO.sub.3 H(2)                                                                      SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(5)         41  OH 1  O --         SO.sub.3 H(2)                                                                      SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(4)         42  OH 2  O --         H    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(3)         43  OH 2  O --         H    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(4)         44  OH 3  O --         H    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(4)         __________________________________________________________________________

EXAMPLE 45

97 parts of a chloro aluminium phthalocyanine tetrasulphochloride formedaccording to a method described in the first paragraph of Example 1 werestirred in 300 parts of water and 100 parts of ice. Thereafter, asolution of 14.5 parts of 1,3-diaminobenzol-monohydrochloride in 100parts of ice water were added. The pH of the resultant solution whichwas 1-2 was adjusted to 4 with 20% sodium hydroxide and the reactionmixture was maintained at 0 to 5° C. for 4 hours.

Thereafter, the reaction mixture was adjusted to pH 10-11 by adding 20%sodium hydroxide and left to stir for a further 2 hours at 60° C. Theproduct was salted out of solution using sodium chloride and theprecipitate filtered to provide a product 45a in its sodium salt form.##STR43##

97 parts of the dyestuff having a formula 45a was were suspended in amixture of 500 parts of water and 25 parts of 30% hydrochloric acid. Tothe resultant suspension was added 100 parts of ice and diazotisationwas effected by the addition of 7 parts of sodium nitrite. Thereafter,36 parts of 1-(3'-sulphatoethylsulphonylphenyl)-3-methyl-5-pyrazolonwere added to the aqueous suspension of the diazonium salt previouslyformed. The mixture was stirred at room temperature and maintained at apH of 6 to 7 by addition of sodium carbonate until dye formation wascompleted. The dyestuff obtained had the following formula ##STR44##

The dyestuff dyed cotton to a brilliant green shade and dyeingsdisplayed excellent fastness properties.

EXAMPLE 46

97 parts of the chloro aluminium phthalocyanine tetrasulphochlorideprepared according to the method described in the first paragraph ofExample 1 was stirred in 300 parts of water and 100 parts of ice. Tothis solution there was added a solution of 14.5 parts of1,3-diaminobenzol-monohydrochloride in 100 parts of ice water. The pH ofthe resultant solution was 1-2 and it was adjusted to a pH of 4 with 20%sodium hydroxide and allowed to stand for 4 hours at a temperature of ofbetween 0° and 5° C.

Thereafter, 7 parts of a 25% ammoniacal solution was added to thereaction mixture, the pH was adjusted to 7 to 8 by adding 20% sodiumhydroxide and the reaction mixture left for 10 hours. Thereafter, the pHwas 10-11 and the reaction mixture was stirred at 60° C. for 2 hourswhereupon the product was formed as a precipitate which was filteredoff. The product 46a was obtained in its sodium salt form. ##STR45##

97 parts of the amino dyestuff 46a was diazotised according to themethod described in Example 45b. Thereafter, 36 parts of1-(3'-sulphatoethylsulphonylphenyl)-5-pyrazolon-3-carboxylic acid wereadded to the aqueous suspension of the diazonium salt previously formed.The mixture was stirred at room temperature and maintained at a pH of 6to 7 by addition of sodium carbonate until dye formation was completed.After the dyestuff was salted out using sodium chloride, filtered offand dried 129 parts of a product 46b was obtained as a dark blue-greenpowder. ##STR46##

This dyestuff dyed cotton in brilliant yellow-green shade and dyeingsdisplayed excellent fastness properties.

EXAMPLE 47

When one substitutes 18.8 parts of 2,4-diaminobenzolsulphonic for1,3-diaminobenzol-monohydrochlorid in a process analogous to Example 46and couple with 36 parts of1-(3'-sulphatoethylsulphonylphenyl)-3-methyl-5-pyrazolone one obtained adyestuff 47. ##STR47##

EXAMPLES 48-58

The following fibre-reactive dyestuffs were formed by employingprocesses analogous to those described in Examples 45 to 47. ##STR48##

                                      TABLE 3                                     __________________________________________________________________________    Ex.                                                                             X  a b NR.sub.1 R.sub.2                                                                      R.sub.4 (Pos.)                                                                     --N═N Pos.                                                                       R.sub.5                                                                           SO.sub.2 B (Pos.)                            __________________________________________________________________________    48                                                                              OH 2 0    --   H    3      CH.sub.3                                                                          SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H                                        (4)                                          49                                                                              OH 3 0    --   H    3      CH.sub.3                                                                          SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H                                        (4)                                          50                                                                              OH 2 0    --   H    3      COOH                                                                              SO.sub.3 CH.sub.2 CH.sub.2 OSO.sub.3 H                                        (3)                                          51                                                                              OH 2 0    --   SO.sub.3 H (4)                                                                     3      CH.sub.3                                                                          SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H                                        (4)                                          52                                                                              OH 2 0    --   SO.sub.3 H (6)                                                                     3      CH.sub.3                                                                          SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H                                        (4)                                          53                                                                              OH 2 0         SO.sub.3 H (3)                                                                     4      COOH                                                                              SO.sub.2 CH═CH.sub.2 (4)                 54                                                                              OH 2 1 NH.sub.2                                                                              SO.sub.3 H (4)                                                                     3      COOH                                                                              SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H                                        (3)                                          55                                                                              OH 2 1 NH.sub.2                                                                              SO.sub.3 H (4)                                                                     3      CH.sub.3                                                                          SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H                                        (4)                                          56                                                                              OH 2 1 NHCH.sub.2 CH.sub.2 OH                                                                H    3      COOH                                                                              SO.sub.2 CH═CH.sub.2 (4)                 57                                                                              OH 2 1 NHCH.sub.2 CH.sub.2 SO.sub.3 H                                                        H    3      CH.sub.3                                                                          SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H                                        (3)                                          58                                                                              OH 2 1         H    3      COOH                                                                              SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H                                        (4)                                          __________________________________________________________________________

EXAMPLE 59

97 parts of the amino dyestuff of Example 45a was mixed with 600 partsof ice water and 18.4 parts of 2,4,6-trichlorotriazine were added withgood stirring. The pH was adjusted to 6-6.5 over 3 hours with 20% sodiumhydroxide. To this mixture was added a solution of(3'-aminobenzolsulphonyl)-2-sulphatoethane in 100 parts of water and theresulatant mixture was stirred for 4 hours whilst being maintained at apH of 6-6.5 with a 15% sodium bicarbonate solution. After salting theproduct out of solution with sodium chloride, filtering and drying acompound 59 was obtained. ##STR49##

EXAMPLE 60

97 parts of the amino dyestuff 46a was mixed in 600 parts of ice waterand 13.5 parts of 2,4,6-trifluorotriazine were added at a temperature offrom -5° to -10° C. The solution was stirred for 3 hours and wasmaintained at a pH of 5 to 6 with 20% sodium hydroxide. A solution of17.2 parts of (2'-aminoethane-1'-sulphonyl)-2-chloroethane in 100 partsof ice water was added to the reaction mixture. The resultant mixturewas stirred for 4 hours and the pH maintained at 6.5 to 7 with 20%sodium hydroxide. After salting the product out of solution using sodiumchloride, filtering and drying, the product 60 was obtained. ##STR50##

EXAMPLE 61 ##STR51##

97 parts of the amino dyestuff 45a was mixed in 600 parts of ice waterand 13.5 parts of 2,4,6-trifluorotriazine were added at a temperature offrom -5° to -10° C. The solution was stirred for 3 hours and wasmaintained at a pH of 5 to 6 with 20% sodium hydroxide. A solution of16.7 parts of (2'-aminopropane-1'-sulphonyl)-ethane-2-ol in 100 parts ofice water was added to the reaction mixture. The resultant mixture wasstirred for 4 hours and the pH maintained at 6.5 to 7 with 20% sodiumhydroxide. After salting the product out of solution using sodiumchloride, filtering and drying, the product 61a was obtained. Thisintermediate was converted to its sulphuric acid half ester as describedin Example 3b. ##STR52##

EXAMPLES 62-73

The following fibre-reactive dyestuffs were obtained following themethod of Examples 59 to 61.

                                      TABLE 4                                     __________________________________________________________________________     ##STR53##                                                                    Ex.                                                                             X  a b NR.sub.1 R.sub.2                                                                      R.sub.4 (Pos.)                                                                     NR.sub.8 (Pos.)                                                                    L  NR.sub.7 R.sub.8                                                                        SO.sub.2 B                            __________________________________________________________________________    62                                                                              OH 3 0 --      H    NH(3)                                                                              F  NHCH.sub.2 CH.sub.2 CH.sub.2                                                            SO.sub.2 CH.sub.2 CH.sub.2                                                    OSO.sub.3 H                           63                                                                              OH 3 0 --      H    NH(3)                                                                              F  NHCHCH.sub.2                                                                            SO.sub.2 CHCH.sub.2                   64                                                                              OH 3 0 --      SO.sub.3 H(4)                                                                      NH(3)                                                                              Cl                                                                                ##STR54##                                                                              SO.sub.2 CH.sub.2 CH.sub.2                                                    OSO.sub.3 H                           65                                                                              OH 3 0 --      SO.sub.3 H(6)                                                                      NH(3)                                                                              Cl                                                                                ##STR55##                                                                              SO.sub.2 CH.sub.2 CH.sub.2                                                    OSO.sub.3 H                           66                                                                              OH 3 0 --      SO.sub.3 H(6)                                                                      NH(3)                                                                              F                                                                                 ##STR56##                                                                              SO.sub.2 CHCH.sub.2                   67                                                                              OH 3 0 --      SO.sub.3 H(3)                                                                      NH(3)                                                                              OH                                                                                ##STR57##                                                                              SO.sub.2 CH.sub.2 CH.sub.2                                                    OSO.sub.3 H                           68                                                                              OH 3 0 --      SO.sub.3 H(6)                                                                      NH(3)                                                                              F  NHCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                  SO.sub.2 CHCH.sub.2                   69                                                                              OH 3 0 --      SO.sub.3 H(6)                                                                      NH(3)                                                                              OH NHCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                  SO.sub.2 CH.sub.2 CH.sub.2                                                    OSO.sub.3 H                           70                                                                              OH 2 1 NH.sub.2                                                                              SO.sub.3 H(4)                                                                      NH(3)                                                                              Cl                                                                                ##STR58##                                                                              SO.sub.2 CH.sub.2 CH.sub.2                                                    OSO.sub.3 H                           71                                                                              OH 2 1 NHCH.sub.2 CH.sub.2 OH                                                                H    NH(3)                                                                              Cl                                                                                ##STR59##                                                                              SO.sub.2 CHCH.sub.2                   72                                                                              OH 2 1 NHCH.sub.2 CH.sub.2 SO.sub.3 H                                                        H    NH(3)                                                                              F                                                                                 ##STR60##                                                                              SO.sub.2 CH.sub.2 CH.sub.2                                                    OSO.sub.3 H                           73                                                                              OH 2 1 morpholino                                                                            H    NH(3)                                                                              F                                                                                 ##STR61##                                                                              SO.sub.2 CH.sub.2 CH.sub.2                                                    OSO.sub.3 H                           __________________________________________________________________________

EXAMPLES 74

20 parts of PcAlCl. 2H₂ O are stirred in 140 parts of chlorosulphonicacid for 30 minutes at 20° to 25° C. The reaction mixture is then heatedto 135° to 140° C. over 2 hours. After 4 hours the reaction mixture iscooled to room temperature using an ice bath. The suspension thus formedis filtered and washed in ice water to remove excess acid.

97 parts of the product formed by the above reaction was stirred in 300parts of water and 100 parts of ice. Thereafter, a solution of(3'-aminobenzosulphonyl)-2-sulphatoethane in 100 parts of ice water isadded (3 moles per 1 mole of phthalocyanine). The pH of the resultantsolution which is 1-2 is increased to 4-5 with 20% sodium hydroxide andthereafter left for 15 hours at a temperature of from 0° to 5° C. Theresulant dyestuff is salted out with sodium chloride, filtered and driedat a temperature of from 40° to 50° C. ##STR62##

The dyestuff dyes cellulosic material, in particular cotton, tobrilliant green shades with excellent wet fastness.

EXAMPLE 75

97 parts of the chlorosulphonated phthalocyanine obtained according tothe methodology of Example 74 is stirred in 300 parts of water and 100parts of ice. Thereafter, a solution of 14.5 parts of 1,3-diaminobenzenemonohydrochloride in 100 parts of ice water is added under stirring. ThepH of the resultant solution which is 1-2 is increased to 4-5 with 20%sodium hydroxide before adding 28.1 parts of(3'-aminobenzosulphonyl)-2-sulphatoethane and reacting for 15 hours at atemperature of from 0° to 5° C. to yield compound 75a. ##STR63##

To the solution of 75a obtained according to the above procedure isadded 14 parts of 2,4,6-trifluoropyrimidine at a pH of 5 to 6(maintained with the addition of 15% sodium carbonate solution). Theresultant dyestuff is salted out with sodium chloride, filtered anddried under vacuum at 40° to 50° C. The resultant dyestuff according tothe formula 75 dyed cotton in brilliant green shades with good fastnessproperties. ##STR64##

EXAMPLES 76 to 88

The compounds of Table 5 were formed according to a process analogous tothe process described in Example 75. All compounds dyed cotton inbrilliant green shades and displayed good fastness properties.

                  TABLE 5                                                         ______________________________________                                         ##STR65##                                                                    Ex  a       SO.sub.2 B(Pos.)                                                                              H, SO.sub.3 H                                                                         NHZ(Pos.)                                 ______________________________________                                        75  2       SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(3)                                                     H       NHZ.sub.3 (3)                             76  1       SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(4)                                                     H       NHZ.sub.3 (3)                             77  2       SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(4)                                                     H       NHZ.sub.4 (3)                             78  1       SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(3)                                                     SO.sub.3 H(4)                                                                         NHZ.sub.3 (3)                             79  1       SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(3)                                                     SO.sub.3 H(4)                                                                         NHZ.sub.4 (3)                             80  1.5     SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(3)                                                     H       NHZ.sub.3 (3)                             81  1       SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(3)                                                     SO.sub.3 H(4)                                                                         NHZ.sub.8 (3)                             82  1.5     SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(3)                                                     SO.sub.3 H(4)                                                                         NHZ.sub.4 (3)                             83  2       SO.sub.2 CHCH.sub.2 (4)                                                                       SO.sub.3 H(4)                                                                         NHZ.sub.4 (3)                             84  2       SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(3)                                                     SO.sub.3 H(4)                                                                         NHZ.sub.5 (3)                             85  2       SO.sub.2 CHCH.sub.2 (3)                                                                       H       NHZ.sub.3 (3)                             86  2       SO.sub.2 CHCH.sub.2 (3)                                                                       H       NHZ.sub.4 (3)                             87  1.5     SO.sub.2 CHCH.sub.2 (3)                                                                       SO.sub.3 H(3)                                                                         NHZ.sub.5 (4)                             88  1       SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H(4)                                                     SO.sub.3 H(3)                                                                         NHZ.sub.5 (4)                             ______________________________________                                    

EXAMPLE 89

The process of Example 75 is followed. However, rather than adding2,4,6-trifluoropyrimidine to the solution of compound 75a, 13.5 parts of2,4,6-trifluorotriazine is added and the condensation reaction iscarried out at 0°-10° C. and at a pH of 4 to 5 (using 15% sodiumcarbonate solution). 9 parts of morpholine is added to the resultantcondensation product at a pH of 5 to 16 and a temperature of 0° to 25°C. The resultant dyestuff having the formula 89 is salted out usingsodium chloride, filtered and dried under vacuum at 40° to 50° C.##STR66##

EXAMPLES 90 to 92

The compounds of Table 6 were formed according a process analogous tothat of Example 89. All compounds dye cotton to brilliant green shadesand displayed good fastness properties.

                  TABLE 6                                                         ______________________________________                                         ##STR67##                                                                                                      H,                                          Ex  a     SO.sub.2 B     A.sub.n  SO.sub.3 H                                                                         NHZ                                    ______________________________________                                        90  1     SO.sub.2 (CH.sub.2).sub.2 OSO.sub.3 H(3)                                                      ##STR68##                                                                             SO.sub.3 H (4)                                                                     NHZ.sub.8 (3)                          91  1     SO.sub.2 CHCH.sub.2                                                                          (CH.sub.2).sub.2 O(CH.sub.2).sub.2                                                     H    NHZ.sub.7 (3)                          92  1     SO.sub.2 CHCH.sub.2                                                                          (CH.sub.2).sub.2 O(CH.sub.2).sub.2                                                     H    NHZ.sub.7 (3)                          ______________________________________                                    

The compounds of Table 7 were formed according to a process analogous tothe process described in Example 75. All compounds dye cotton tobrilliant green shades.

                  TABLE 7                                                         ______________________________________                                         ##STR69##                                                                                                            NHZ                                   Ex.- a      A.sub.n      SO.sub.2 B                                                                            H, SO.sub.3 H                                                                        (Pos.)                                ______________________________________                                        93   1      CH.sub.2 CH.sub.2                                                                          CHCH.sub.2                                                                            SO.sub.3 H(4)                                                                        NHZ.sub.3 (3)                         94   1      CH.sub.2 CH.sub.2 CH.sub.2                                                                 CHCH.sub.2                                                                            H      NHZ.sub.3 (3)                         95   1.5    CH.sub.2 CH.sub.2                                                                          CHCH.sub.2                                                                            H      NHZ.sub.4 (3)                         96   2      CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                       CH.sub.2 CH.sub.2 Cl                                                                  H      NHZ.sub.3 (3)                         97   1.5    CH.sub.2 CH.sub.2 CH.sub.2                                                                 CH.sub.2 CH.sub.2 Cl                                                                  SO.sub.3 H(4)                                                                        NHZ.sub.5 (3)                         98   2      CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                       CHCH.sub.2                                                                            H      NHZ.sub.3 (3)                         99   1      CH.sub.2 CH.sub.2 CH.sub.2                                                                 CHCH.sub.2                                                                            SO.sub.3 H(4)                                                                        NHZ.sub.4 (3)                         100  1.5    CH.sub.2 CH.sub.2 CH.sub.2                                                                 CHCH.sub.2                                                                            H      NHZ.sub.5 (3)                         ______________________________________                                    

EXAMPLE 101

A compound corresponding to Example 75a is diazotised according to theprocedure of Example 16 in German Patent DOS 1 9521056. The diazoniumsalt suspension was poured onto a solution of 300 parts of ice water and20 parts of 1-(3'-methylaminopropyl)-6-hydroxy-4-methylpyridone-(2) at0° to 5° C. The pH is maintained at 6.5 to 7.5 with additions of 15%sodium carbonate solution. 24 parts of 5-cyano-2,4,6-trichloropyrimidineare added to the resultant reaction mixture at 20° to 30° C. whilstmaintaining the pH at a constant 7.5-8 with additions of 15% sodiumcarbonate solution. The resultant dyestuff is salted out using sodiumchloride, filtered and dried under vacuum at 40° to 50° C. to yieled thedyestuff having the formula 101 ##STR70##

EXAMPLES 102 to 105

The compounds in Table 8 are formed by a process analogous to thatdescribed in Example 101. All compounds dye cotton to green shades anddisplayed good fastness properties.

                  TABLE 8                                                         ______________________________________                                         ##STR71##                                                                    Ex.  a      H, SO.sub.3 H                                                                          Z   NN(Pos.) SO.sub.2 B(Pos.)                            ______________________________________                                        102  1      SO.sub.3 H(4)                                                                          Z.sub.5                                                                           3        SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H(4)                                        103  1.5    SO.sub.3 H(4)                                                                          Z.sub.5                                                                           3        SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H(3)                                        104  2      SO.sub.3 H(4)                                                                          Z.sub.5                                                                           3        SO.sub.2 CHCH.sub.2 (4)                     105  2      SO.sub.3 H(4)                                                                          Z.sub.5                                                                           3        SO.sub.2 CHCH.sub.2 (5)                     ______________________________________                                    

EXAMPLE 106 to 110

The compounds of Table 9 were formed according to a process analogous tothe process described in Example 101. All compounds dye cotton to greenshades and displayed good fastness properties.

                                      TABLE 9                                     __________________________________________________________________________     ##STR72##                                                                    Ex.  a    H, SO.sub.3 H)                                                                       Z.sub.                                                                              NN(Pos.) SO.sub.2 B(Pos.)                              __________________________________________________________________________    106  1    SO.sub.3 H(4)                                                                        Z.sub.9                                                                             3        SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H(3)                                          107  1    SO.sub.3 H(4)                                                                        Z.sub.9                                                                             3        SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H(4)                                          108  1.5  SO.sub.3 H(4)                                                                        Z.sub.9                                                                             3        SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H(3)                                          109  1.5  SO.sub.3 H(4)                                                                        Z.sub.9                                                                             3        SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H(4)                                          110  2    SO.sub.3 H(4)                                                                        Z.sub.5                                                                             3        SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3          __________________________________________________________________________                                    H(4)                                      

EXAMPLE 111

The process according to Example 75 is followed with the modificationthat instead of using 28.1 parts of3'-aminobenzenesulphonyl)-2-sulphoethane one uses 50 parts of a compoundaccording to the formula 111 a ##STR73##

Therafter, 14 parts of 2,4,6-trifluoropyrimidine are added to thereaction mixture whilst maintaining the pH constant at 5 to 6 withadditions of 15% sodium carbonate solution. The resultant product wassalted out with sodium chloride, filtered and dried in a vacuum at 40 to50° C. to yield the dyestuff of the formula 111 which dyes cotton tobrilliant green shades and has good fastness properties. ##STR74##

EXAMPLES 112 to 116

The compounds of Table 10 were formed according to a process analogousto the process described in Example 111. All the compounds dye cotton tobrilliant green shades.

                                      TABLE 10                                    __________________________________________________________________________     ##STR75##                                                                           (H,  CH.sub.3,      H, SO.sub.3 H                                                                      NHZ                                           Ex.                                                                              a   SO.sub.3 H)*                                                                       COOH SO.sub.3 B (Pos.)                                                                       (Pos.)                                                                             (Pos.)                                        __________________________________________________________________________    112                                                                              1   SO.sub.3 H(4)                                                                      CH.sub.3                                                                           CH.sub.2 CH.sub.2 OSO.sub.3 H(4)                                                        H    NHZ.sub.3 (3)                                 113                                                                              1.5 SO.sub.3 H(4)                                                                      COOH CHCH.sub.2 (4)                                                                          H    NHZ.sub.4 (3)                                 114                                                                              2   H    CH.sub.3                                                                           CH.sub.2 CH.sub.2 OSO.sub.3 H(3)                                                        H    NHZ.sub.3 (3)                                 115                                                                              1.5 H    COOH CH.sub.2 CH.sub.2 OSO.sub.3 H(4)                                                        SO.sub.3 H(4)                                                                      NHZ.sub.5 (3)                                 116                                                                              2   SO.sub.3 H(4)                                                                      CH.sub.3                                                                           CH.sub.2 CH.sub.2 OSO.sub.3 H                                                           SO.sub.4 H(4)                                                                      NHZ.sub.3 (3)                                 __________________________________________________________________________

                  TABLE 11                                                        ______________________________________                                        UV absorbances measured in water (λmax/nm)                                     Ex.  λmax                                                      ______________________________________                                                 1   672                                                                       2   675                                                                       3   668                                                                       4   667                                                                       5   671                                                                       6   669                                                                       7   670                                                                       8   670                                                                       9   665                                                                      10   668                                                                      11   664                                                                      12   667                                                                      13   668                                                                      14   671                                                                      15   669                                                                      16   670                                                                      17   665                                                                      18   666                                                                      19   668                                                                      20   663                                                                      21   668                                                                      22   670                                                                      23   667                                                                      24   666                                                                      25   672                                                                      26   672                                                                      27   660                                                                      28   670                                                                      29   671                                                                      30   673                                                                      31   674                                                                      32   668                                                                      33   667                                                                      34   669                                                                      35   670                                                                      36   665                                                                      37   671                                                                      38   670                                                                      39   665                                                                      40   672                                                                      41   673                                                                      42   664                                                                      43   669                                                                      44   674                                                                      45   671                                                                      46   664                                                                      47   669                                                                      48   672                                                                      49   670                                                                      50   665                                                                      51   676                                                                      52   664                                                                      53   671                                                                      54   668                                                                      55   664                                                                      56   667                                                                      57   667                                                                      58   665                                                                      59   671                                                                      60   669                                                                      61   670                                                                      62   674                                                                      63   675                                                                      64   666                                                                      65   672                                                                      66   670                                                                      67   671                                                                      68   661                                                                      69   673                                                                      70   671                                                                      71   665                                                                      72   672                                                                      73   671                                                                      74   667                                                                      75   669                                                                      76   665                                                                      77   675                                                                      78   674                                                                      79   667                                                                      80   668                                                                      81   672                                                                      82   665                                                                      83   668                                                                      84   663                                                                      85   669                                                                      86   673                                                                      87   666                                                                      88   668                                                                      89   672                                                                      90   667                                                                      91   665                                                                      92   668                                                                      93   673                                                                      94   665                                                                      95   667                                                                      96   675                                                                      97   673                                                                      98   670                                                                      99   670                                                                      100  669                                                                      101  663                                                                      102  665                                                                      103  666                                                                      104  672                                                                      105  669                                                                      106  672                                                                      107  667                                                                      108  670                                                                      109  668                                                                      110  667                                                                      111  671                                                                      112  668                                                                      113  666                                                                      114  672                                                                      115  664                                                                      116  668                                                              ______________________________________                                    

Application Example A

To a dye bath consisting of 100 g of demineralized water, 0.25 g of thedyestuff of Example 1 and 10 g of cotton tricot (bleached) are added.The dyebath is heated to 50° C. over a 10 minutes period and maintainedat this temperature for 25 minutes. Thereafter, 0.4 g of calcinatedsodium carbonate and 0.3 ml of concentrated caustic soda-solution areadded. After 30 minutes at 50° C. the temperature is increased to 60° C.over a 25 minutes period and dyeing is continued for 60 minutes at thistemperature. The dyed cotton fabric is removed from the liquor, rinsedfor 10 minutes in 500 g of demineralized water in the presence of 0.25 gof a non-ionic surfactant. Finally the cotton dyeing is rinsed anddried. The green dyeing obtained displays good all-round fastness.

The Example is repeated with the compound of Example 74. The greendyeing obtained displays good all round fastness properties.

Application Example B

A printing paste having the components

40 parts of the dyestuff of the Example 1

100 parts of urea

350 parts of water

500 parts of a 4% sodium alginate thickener

10 parts of sodium bicarbonate

₋₋₋₋₋₋

1000 parts in all

was applied to cotton material by a conventional printing process.

The printed and dried material was steamed for 4 to 8 minutes at 102° to105° C. and then given a cold and hot rinse. The fixed cotton materialwas then washed twice for 10 minutes, each time in 5000 parts ofboiling, demineralised water, subsequently rinsed for 2 minutes inrunning, demineralised water of 60° C.±10° C., 1 minute in running tapwater of 60° C. ±10° C. and for 1 minute in cold tap water.

The Example was repeated for the compound of Example 74.

We claim:
 1. Compounds of formula (I) ##STR76## and their saltswherein,R₁ is hydrogen, or an open chain hydrocarbon group having from 1to 8 carbon atoms or an open chain hydrocarbon group having 1 to 8carbon atoms comprising oxygen, nitrogen or sulphur atoms, R₂ is,independently of R₁, any of the significances of R₁ or is a group--A_(n) SO₂ --B or --A_(n) SO₂ --B' wherein B is selected from ant ofthe groups according to the formula

    --CH═CH.sub.2, --CH.sub.2 CH--Y, --CH═CH--Y or --CH(CH.sub.2 Y)--CH.sub.2 Y

wherein Y represents a hydroxyl group or a group selected from halogen,--OSO₃ H or --SO₃ H, --OPO₂ H₂, --SSO₃ H, --OCOCH₃, --OCOC₅ H₅,--OCO(CH₂)₂ --COOH, --OCO--CH═CH--COOH, --OCO--C6H4--COOH, OCO--COOH,--OSO₂ CH₃, a quaternary nitrogen group, or bivalent groups--OCO--COO--, --OCO--(CH₂)₂ --COO--, --OCO--CH═CH--COO and OCO--C₆ H₄--COO--,or R1 and R2 taken together form a 3 to 6 carbon heterocyclicring also comprising Nitrogen and optionally oxygen: B' is --(CH₂)₂--OSO₃ H and A_(n) is A₁ to A₃ wherein A₁ is a group ##STR77## wherein *is a bond connected to SO₂ B and R₃ is a direct bond or is --(CH₂)₂--,A₂ is a group A1 in which R₃ is a direct bond or is an alkylene oroxyalkylene group having from 2 to 4 carbon atoms, and A₃ is a grouprepresented by the formula ##STR78## (wherein * is a bond connected toSO₂ B) R₁ and R₂ together represent a divalent alkylene or aralkylenegroup, or a divalent alkylene or aralkylene group bearing oxygen,nitrogen or sulphur atoms, R_(a) is hydrogen, alkyl having 1 to 4 carbonatoms, hydroxyalkyl having 2 to 4 carbon atoms or a group --A_(x) SO₂--B wherein B is as hereinabove defined and A_(x) is defined below, RGis a group containing a fibre-reactive group and is selected from--A_(x) SO₂ --B or --D--NR₁₀ Zwherein A_(x) is represented by a divalenthydrocarbon group or a divalent hydrocarbon group comprising oxygen,nitrogen or sulphur atoms; or an aza-alkylene group --(CH₂)₂ --NR₄--(CH₂)₂ -- wherein R₄ is a C₁₋₄ alkyl group or a C₁₋₄ alkyl groupsubstituted with a hydroxyl group; an arylene group ##STR79## wherein R₅represents a hydrogen atom, halogen atom, an alkyl group having 1 to 4carbon atoms, an alkoxy group having 1 to 4 carbon atoms, --SO₃ H or--COOH; phenylene azophenylpyrazolaryl group according to the formula##STR80## wherein R₅ is as hereinbefore defined and R6 is a methyl groupor a group --COOH; or a triazine group according to the formula##STR81## wherein L is a hydroxyl group, a halogen atom, or an aminogroup NR₁ R'₂ wherein R₂ is any of the significances of R₁ or togetherwith R₁ is a divalent alkylene or aralkylene group or a divalentalkylene or aralkylene group bearing an oxygen, nitrogen or sulphuratom, or a pyridinium group ##STR82## wherein R₉ is --SO₃ H or --COOH,R₇ is a divalent group selected from alkylene, oxaalkylene, arylene oraralkylene, R₈ is a hydrogen atom, an alkyl group having 1 to 4 carbonatoms, or a hydroxyalkyl group having 2 to 4 carbon atoms, Z representsa heterocyclic fibre-reactive radical selected from halo-triazine orhalo-pyrimidine having a labile fluorine or chlorine atom R₁₀ is H orCh3 and D represents a divalent residue selected from ##STR83## M isAlOH or AlCl Pc is a phthalocyanine radical a is 1, 2or3 b is 0, 1, 2or3c is 0, 1 or2 and a+b+c has a value which is greater than or equal to 3and less than or equal to 4 and b and c cannot be zero at the same time,with the provisos that,i) when c is 1 or 2, RG is --D--NR₁₀ Z and D isD₁, then b is 1 or 2, R₂ is --A2SO₂ -- B and R_(a) is not A_(x) SO₂ --Bii) when c is 1, RG is --D--NR₁₀ Z and D is D₂ or D₃, then be is 1 or 2,R₂ is --A₂ SO₂ -- B and R_(a) is not A_(x) SO₂ --B, iii) when c is 1, RGis --D--NR₁₀ Z and D is D₁ then b is 1, R₂ is --A₃ SO₂ -- B and R_(a) isnot A_(x) SO₂ --B, iv) when c is 1 and RG is A_(x) SO₂ --B, then R₂ isindependently of R₁, any of the significances of R₁, and v) when c iszero, then b is 1 or 2, R₂ is A₁ SO₂ --B'.
 2. Compounds according toclaim 1 and their salts wherein the group Z is selected from thefiber-reactive radicals Z₁ to Z₉ defined hereinbelow ##STR84## 3.Compounds according to claim 1 or claim 2 having the formula (Ia)##STR85## and their salts wherein A_(x), M, Pc, R_(a), R₁ and R₂together and B are as defined in claim 1, R₁ and R₂ are independentlyhydrogen, a hydrocarbon group having from 1 to 8 carbon atoms or ahydrocarbon group having from 1 to 8 carbon atoms comprising oxygen,nitrogen or sulphur atoms, and a has a value of 1, 2 or 3 and b has avalue of 0, 1 or 2 provided that a+b is not greater than
 3. 4. Compoundsaccording to claim 2 of the formula (Ib) ##STR86## and their salts,wherein Pc, A₁, M and B' are as defined in claim 1 and a is 1, 2 or 3, bis 1, 2 or 3 and a+b is a value of 3 or
 4. 5. Compounds according toclaim 4 having the formula (Ib) ##STR87## and their salts.
 6. Compoundsaccording to claim 2 having the formula (Ic) ##STR88## and their saltswherein the symbols Pc, M, Z, A₂, R₁, B and a are as defined in claim 1or claim 2, R₁₁ is hydrogen or --SO₃ H, c is 1 or 2 and b is 1 or 2,provided that a+b+c is 3 or
 4. 7. Compounds according to claim 6 theirsalts and mixtures thereof wherein A₂ is represented by phenylene,--(CH₂)_(n) --, wherein n is 2 or 3 or --(CH₂)₂ --O--(CH₂)₂ --. 8.Compounds according to claim 6 their salts and mixtures thereof whereinB is represented by --CH₂ CH₂ OSO₃ H, CH₂ CH₂ Cl or --CH═CH₂,. 9.Compounds according to claim 6, their salts and mixtures thereof whereinA₂ is phenylene when B is --CH₂ CH₂ OSO₃ H and A₂ is --(CH₂)_(n) --,wherein n is 2 or 3 or --(CH₂)₂ --O--(CH₂)₂ -- when B is --CH₂ CH₂ Cl or--CH═CH₂.
 10. Compounds according to claim 1 having the formula (Id)##STR89## and their salts, wherein the symbols D, Z, B, Pc, M, A_(n),R₁₀ are as described in claim 1 and a has a value of 1 or
 2. 11.Compounds according to claim 10, and their salts wherein the group A_(n)is A₁, D is D₂, B is --CH₂ CH₂ OSO₃ H or --CH═CH₂ and Z is Z₅ ; A_(n) isA₁, D is D₃, B is --CH₂ CH₂ OSO₃ H and Z is Z₅ or Z₉ ; and A_(n) is A₃,D is D₁, B is --CH₂ CH₂ OSO₃ H or --CH═CH₂ and Z is Z₃, Z₄ or Z₅. 12.Compounds of the following formulas:

    __________________________________________________________________________     ##STR90##                                                                     ##STR91##                                                                     ##STR92##                                                                     ##STR93##                                                                     ##STR94##                                                                    Ex.                                                                             X  a b NR.sub.1 R.sub.2                                                                         R.sub.a    A.sub.z  B                                     __________________________________________________________________________     4                                                                              OH 2 1 NH.sub.2   H          CH.sub.2 CH.sub.2                                                                      CHCH.sub.2                             5                                                                              OH 2 1 NH.sub.2   H          CH.sub.2 CH.sub.2                                                                      CH.sub.2 CH.sub.2 Cl                   6                                                                              OH 2 1 NH.sub.2   H          CH.sub.2 CH.sub.2 CH.sub.2                                                             CHCH.sub.2                             7                                                                              OH 2 1 NH.sub.2   H          CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                   CH.sub.2 CH.sub.2 Cl                   8                                                                              Cl 2 1 NH.sub.2   H          CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                   CHCH.sub.2                             9                                                                              OH 2 1 NH.sub.2   CH.sub.2 CH.sub.2 SO.sub.2 CHCH.sub.2                                                    CH.sub.2 CH.sub.2                                                                      CHCH.sub.2                            10                                                                              OH 2 1 NHCH.sub.3 H          CH.sub.2 CH.sub.2                                                                      CH.sub.2 Cl                           11                                                                              OH 2 1 NH.sub.2   H                                                                                         ##STR95##                                                                             CH.sub.2 CH.sub.2 Cl                  12                                                                              OH 2 1 NH.sub.2   H                                                                                         ##STR96##                                                                             CHCH.sub.2                            13                                                                              OH 2 1 NHCH.sub.2 CH.sub.2 OH                                                                   H          CH.sub.2 CH.sub.2                                                                      CHCH.sub.2                            14                                                                              OH 2 1 NHCH.sub.2 CH.sub.2 OSO.sub.3 H                                                          H          CH.sub.2 CH.sub.2                                                                      CH.sub.2 CH.sub.2 OSO.sub.3 H         15                                                                              OH 2 1 NHCH.sub.2 CH.sub.2 SO.sub.3 H                                                           H          CH.sub.2 CH.sub.2                                                                      CHCH.sub.2                            16                                                                              OH 2 1 N(CH.sub.3)CH.sub.2 CH.sub.2 SO.sub.3 H                                                  H          CH.sub.2 CH.sub.2                                                                      CHCH.sub.2                            17                                                                              OH 2 1            H          CH.sub.2 CH.sub.2                                                                      CHCH.sub.2                            18                                                                              OH 2 1 N(CH.sub.3)CH.sub.2 CH.sub.2 OH                                                          H          CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                   CHCH.sub.2                            19                                                                              OH 2 1 NHCH.sub.2 CH.sub.2 CH.sub.2 OH                                                          H          CH.sub.2 CH.sub.2                                                                      CHCH.sub.2                            20                                                                              OH 2 0            H          CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                   CHCH.sub.2                            21                                                                              OH 2 0            H          CH.sub.2 CH.sub.2                                                                      CHCH.sub.2                            22                                                                              OH 3 0            H          CH.sub.2 CH.sub.2 CH.sub.2                                                             CH.sub.2 CH.sub.2 Cl                  23                                                                              OH 3 0            H          CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                   CH.sub.2 CH.sub.2 Cl                  __________________________________________________________________________     ##STR97##                                                                     ##STR98##                                                                     ##STR99##                                                                     ##STR100##                                                                    ##STR101##                                                                    ##STR102##                                                                    ##STR103##                                                                   Ex.  X    a  b   NR.sub.1 R.sub.2                                                                          R.sub.4 (Pos.)                                                                       SO.sub.2 B (Pos.)                         __________________________________________________________________________    27   OH   2  1   NH.sub.2    H      SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (3)                                     28   OH   2  1   NH.sub.2    H      SO.sub.2 CHCH.sub.2 (3)                   29   OH   2  1   NHCH.sub.2 CH.sub.2 OH                                                                    H      SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (4)                                     30   OH   2  1   NHCH.sub.2 CH.sub.2 OH                                                                    H      SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (3)                                     31   OH   2  1   NHCH.sub.2 CH.sub.2 SO.sub.3 H                                                            H      SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (4)                                     32   OH   2  1   N(CH.sub.3)CH.sub.2 CH.sub.2 SO.sub.3 H                                                   H      SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (3)                                     33   OH   2  1                                                                                  ##STR104## H      SO.sub.2 CHCH.sub.2 (4)                   34   OH   2  1   N(CH.sub.3)CH.sub.2 CH.sub.2 OH                                                           H      SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (4)                                     35   OH   2  1   N(CH.sub.3)CH.sub.2 CH.sub.2 OH                                                           H      SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (3)                                     36   OH   2  1   NHCH.sub.2 CH.sub.2 (OH)CH.sub.3                                                          H      SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (4)                                     37   OH   2  1   NHCH.sub.2 CH.sub.2 CH.sub.2 OH                                                           H      SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (4)                                     38   OH   2  1   NHCH.sub.2 CH.sub.2 CH.sub.2 OH                                                           H      SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (3)                                     39   OH   2  1   NHCH.sub.2 CH.sub.2 COOH                                                                  H      SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (4)                                     40   OH   1  0   --          SO.sub.3 H (2)                                                                       SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (5)                                     41   OH   1  0   --          SO.sub.3 H (2)                                                                       SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (4)                                     42   OH   2  0   --          H      SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (3)                                     43   OH   2  0   --          H      SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (4)                                     44   OH   3  0   --          H      SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (4)                                     __________________________________________________________________________     ##STR105##                                                                    ##STR106##                                                                    ##STR107##                                                                    ##STR108##                                                                    ##STR109##                                                                    ##STR110##                                                                   Ex.                                                                              X  a  b NR.sub.1 R.sub.2                                                                       R.sub.4 (Pos.)                                                                     NN Pos. R.sub.5                                                                           SO.sub.2 B (Pos.)                        __________________________________________________________________________    48 OH 2  0 --       H    3       CH.sub.3                                                                          SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (4)                                    49 OH 3  0 --       H    3       CH.sub.3                                                                          SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (4)                                    50 OH 2  0 --       H    3       COOH                                                                              SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (3)                                    51 OH 2  0 --       SO.sub.3 H (4)                                                                     3       CH.sub.3                                                                          SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (4)                                    52 OH 2  0 --       SO.sub.3 H (6)                                                                     3       CH.sub.3                                                                          SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (4)                                    53 OH 2  0          SO.sub.3 H (3)                                                                     4       COOH                                                                              SO.sub.2 CHCH.sub.2 (4)                  54 OH 2  1 NH.sub.2 SO.sub.3 H (4)                                                                     3       COOH                                                                              SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (3)                                    55 OH 2  1 NH.sub.2 SO.sub.3 H (4)                                                                     3       CH.sub.3                                                                          SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (4)                                    56 OH 2  1 NHCH.sub.2 CH.sub.2 OH                                                                 H    3       COOH                                                                              SO.sub.2 CHCH.sub.2 (4)                  57 OH 2  1 NHCH.sub.2 CH.sub.2 SO.sub.3 H                                                         H    3       CH.sub.3                                                                          SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (3)                                    58 OH 2  1          H    3       COOH                                                                              SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                          H (4)                                    __________________________________________________________________________     ##STR111##                                                                    ##STR112##                                                                    ##STR113##                                                                    ##STR114##                                                                    ##STR115##                                                                   Ex.                                                                             X  a b NR.sub.1 R.sub.2                                                                      R.sub.4 (Pos.)                                                                     NR.sub.7 (Pos.)                                                                    L  NR.sub.7 R.sub.8                                                                        SO.sub.2 B                            __________________________________________________________________________    62                                                                              OH 3 0 --      H    NH (3)                                                                             F  NHCH.sub.2 CH.sub.2 CH.sub.2                                                            SO.sub.2 CH.sub.2 CH.sub.2                                                    OSO.sub.3 H                           63                                                                              OH 3 0 --      H    NH (3)                                                                             F  NHCHCH.sub.2                                                                            SO.sub.2 CHCH.sub.2                   64                                                                              OH 3 0 --      SO.sub.3 H (4)                                                                     NH (3)                                                                             Cl           SO.sub.2 CH.sub.2 CH.sub.2                                                    OSO.sub.3 H                           65                                                                              OH 3 0 --      SO.sub.3 H (6)                                                                     NH (3)                                                                             Cl "         SO.sub.2 CH.sub.2 CH.sub.2                                                    OSO.sub.3 H                           66                                                                              OH 3 0 --      SO.sub.3 H (6)                                                                     NH (3)                                                                             F  "         SO.sub.2 CHCH.sub.2                   67                                                                              OH 3 0 --      SO.sub.3 H (3)                                                                     NH (3)                                                                             OH "         SO.sub.2 CH.sub.2 CH.sub.2                                                    OSO.sub.3 H                           68                                                                              OH 3 0 --      SO.sub.3 H (6)                                                                     NH (3)                                                                             F  NHCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                  SO.sub.2 CHCH.sub.2                   69                                                                              OH 3 0 --      SO.sub.3 H (6)                                                                     NH (3)                                                                             OH NHCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                  SO.sub.2 CH.sub.2 CH.sub.2                                                    OSO.sub.3 H                           70                                                                              OH 2 1 NH.sub.2                                                                              SO.sub.3 H (4)                                                                     NH (3)                                                                             Cl           SO.sub.2 CH.sub.2 CH.sub.2                                                    OSO.sub.3 H                           71                                                                              OH 2 1 NHCH.sub.2 CH.sub.2 OH                                                                H    NH (3)                                                                             Cl           SO.sub.2 CHCH.sub.2                   72                                                                              OH 2 1 NHCH.sub.2 CH.sub.2 SO.sub.3 H                                                        H    NH (3)                                                                             F            SO.sub.2 CH.sub.2 CH.sub.2                                                    OSO.sub.3 H                           73                                                                              OH 2 1         H    NH (3)                                                                             F            SO.sub.2 CH.sub.2 CH.sub.2                                                    OSO.sub.3 H                           __________________________________________________________________________     ##STR116##                                                                    ##STR117##                                                                    ##STR118##                                                                    ##STR119##                                                                   Ex        a    SO.sub.2 B (Pos.)                                                                            H, SO.sub.3 H                                                                          NHZ (Pos.)                             __________________________________________________________________________    75        2    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H (3)                                                   H        NHZ.sub.3 (3)                          76        1    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H (4)                                                   H        NHZ.sub.3 (3)                          77        2    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H (4)                                                   H        NHZ.sub.4 (3)                          78        1    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H (3)                                                   SO.sub.3 H (4)                                                                         NHZ.sub.3 (3)                          79        1    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H (3)                                                   SO.sub.3 H (4)                                                                         NHZ.sub.4 (3)                          80        1.5  SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H (3)                                                   H        NHZ.sub.3 (3)                          81        1    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H (3)                                                   SO.sub.3 H (4)                                                                         NHZ.sub.8 (3)                          82        1.5  SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H (3)                                                   SO.sub.3 H (4)                                                                         NHZ.sub.4 (3)                          83        2    SO.sub.2 CHCH.sub.2 (4)                                                                      SO.sub.3 H (4)                                                                         NHZ.sub.4 (3)                          84        2    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H (3)                                                   SO.sub.3 H (4)                                                                         NHZ.sub.5 (3)                          85        2    SO.sub.2 CHCH.sub.2 (3)                                                                      H        NHZ.sub.3 (3)                          86        2    SO.sub.2 CHCH.sub.2 (3)                                                                      H        NHZ.sub.4 (3)                          87        1.5  SO.sub.2 CHCH.sub.2 (3)                                                                      SO.sub.3 H (3)                                                                         NHZ.sub.5 (4)                          88        1    SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H (4)                                                   SO.sub.3 H (3)                                                                         NHZ.sub.5 (4)                          __________________________________________________________________________     ##STR120##                                                                    ##STR121##                                                                   Ex    a   SO.sub.2 B    A.sub.n  H, SO.sub.3 H                                                                        NHZ                                   __________________________________________________________________________    90    1   SO.sub.2 (CH.sub.2).sub.2 OSO.sub.3 H (3)                                                    ##STR122##                                                                            SO.sub.3 H (4)                                                                       NHZ.sub.8 (3)                         91    1   SO.sub.2 CHCH.sub.2                                                                         (CH.sub.2).sub.2 O(CH.sub.2).sub.2                                                     H      NHZ.sub.7 (3)                         92    2   "             "        H      "                                     __________________________________________________________________________     ##STR123##                                                                   Ex.-    a   A.sub.n     SO.sub.2 B                                                                            H, SO.sub.3 H                                                                         NHZ (Pos.)                            __________________________________________________________________________    93      1   CH.sub.2 CH.sub.2                                                                         CHCH.sub.2                                                                            SO.sub.3 H (4)                                                                        NHZ.sub.3 (3)                         94      1   CH.sub.2 CH.sub.2 CH.sub.2                                                                CHCH.sub.2                                                                            H       NHZ.sub.3 (3)                         95      1.5 CH.sub.2 CH.sub.2                                                                         CHCH.sub.2                                                                            H       NHZ.sub.4 (3)                         96      2   CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                      CH.sub.2 CH.sub.2 Cl                                                                  H       NHZ.sub.3 (3)                         97      1.5 CH.sub.2 CH.sub.2 CH.sub.2                                                                CH.sub.2 CH.sub.2 Cl                                                                  SO.sub.3 H (4)                                                                        NHZ.sub.5 (3)                         98      2   CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                      CHCH.sub.2                                                                            H       NHZ.sub.3 (3)                         99      1   CH.sub.2 CH.sub.2 CH.sub.2                                                                CHCH.sub.2                                                                            SO.sub.3 H (4)                                                                        NHZ.sub.4 (3)                         100     1.5 CH.sub.2 CH.sub.2 CH.sub.2                                                                CHCH.sub.2                                                                            H       NHZ.sub.5 (3)                         __________________________________________________________________________     ##STR124##                                                                    ##STR125##                                                                   Ex.     a   SO.sub.3 H (Pos.)                                                                     Z   NN (Pos.)  SO.sub.2 B (Pos.)                          __________________________________________________________________________    102     1   SO.sub.3 H (4)                                                                        Z.sub.5                                                                           3          SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H                                        (4)                                        103     1.5 SO.sub.3 H (4)                                                                        Z.sub.5                                                                           3          SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H                                        (3)                                        104     2   SO.sub.3 H (4)                                                                        Z.sub.5                                                                           3          SO.sub.2 CHCH.sub.2 (4)                    105     2   SO.sub.3 H (4)                                                                        Z.sub.5                                                                           3          SO.sub.2 CHCH.sub.2 (5)                    __________________________________________________________________________     ##STR126##                                                                   Ex.     a   SO.sub.3 H (Pos.)                                                                     Z   NN (Pos.)  SO.sub.2 B (Pos.)                          __________________________________________________________________________    106     1   SO.sub.3 H (4)                                                                        Z.sub.9                                                                           3          SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H                                        (3)                                        107     1   SO.sub.3 H (4)                                                                        Z.sub.9                                                                           3          SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H                                        (4)                                        108     1.5 SO.sub.3 H (4)                                                                        Z.sub.9                                                                           3          SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H                                        (3)                                        109     1.5 SO.sub.3 H (4)                                                                        Z.sub.9                                                                           3          SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H                                        (3)                                        110     2   SO.sub.3 H (4)                                                                        Z.sub.5                                                                           3          SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H                                        (4)                                        __________________________________________________________________________     ##STR127##                                                                    ##STR128##                                                                    ##STR129##                                                                   Ex.   a  (H, SO.sub.3 H)*                                                                     CH.sub.3, COOH                                                                       SO.sub.2 B (Pos.)                                                                       H, SO.sub.3 H (Pos.)                                                                  NHZ (Pos.)                           __________________________________________________________________________    112   1  SO.sub.3 H (4)                                                                       CH.sub.3                                                                             CH.sub.2 CH.sub.2 OSO.sub.3 H (4)                                                       H       NHZ.sub.3 (3)                        113   1.5                                                                              SO.sub.3 H (4)                                                                       COOH   CHCH.sub.2 (4)                                                                          H       NHZ.sub.4 (3)                        114   2  H      CH.sub.3                                                                             CH.sub.2 CH.sub.2 OSO.sub.3 H (3)                                                       H       NHZ.sub.3 (3)                        115   1.5                                                                              H      COOH   CH.sub.2 CH.sub.2 OSO.sub.3 H (4)                                                       SO.sub.3 H (4)                                                                        NHZ.sub.5 (3)                        116   2  SO.sub.3 H (4)                                                                       CH.sub.3                                                                             CH.sub.2 CH.sub.2 OSO.sub.3 H                                                           SO.sub.4 H (4)                                                                        NHZ.sub.3 (3)                        __________________________________________________________________________